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5,20-Bis(ethoxycarbonyl)-Substituted Antiaromatic [28]Hexaphyrin and Its Bis-NiII and Bis-CuII Complexes
Akito Nakai1, Jinseok Kim2, Dongho Kim2
1Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
Abstract:
5,20-Bis(ethoxycarbonyl)-[28]hexaphyrin was synthesized by acid catalyzed cross-condensation of meso-diaryl-substituted tripyrrane and ethyl 2-oxoacetate followed by subsequent oxidation. This hexaphyrin was found to be a stable 28π-antiaromatic compound with a dumbbell-like conformation. Upon oxidization with PbO2 , this [28]hexaphyrin was converted into an aromatic [26]hexaphyrin with a rectangular shape bearing two ester groups at the edge side. The [28]hexaphyrin can incorporate two NiII or CuII metals by using the ester carbonyl groups and three pyrrolic nitrogen atoms to give bis-NiII and bis-CuII complexes with essentially the same dumbbell-like structure. The antiaromatic properties of the [28]hexaphyrin and its metal complexes have been well characterized.
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